Photolysis of Fluorinated Graphites with Embedded Acetonitrile Using a White-Beam Synchrotron Radiation

Fluorinated graphitic layers with good mechanical and chemical stability, polar C–F bonds, and tunable bandgap are attractive for a variety of applications. In this work, we investigated the photolysis of fluorinated graphites with interlayer embedded acetonitrile, which is the simplest representative of the acetonitrile-containing photosensitizing family. The samples were continuously illuminated in situ with high-brightness non-monochromatized synchrotron radiation. Changes in the compositions of the samples were monitored using X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The NEXAFS N K-edge spectra showed that acetonitrile dissociates to form HCN and N2 molecules after exposure to the white beam for 2 s, and the latter molecules completely disappear after exposure for 200 s. The original composition of fluorinated matrices CF0.3 and CF0.5 is changed to CF0.10 and GF0.17, respectively. The highly fluorinated layers lose fluorine atoms together with carbon neighbors, creating atomic vacancies. The edges of vacancies are terminated with the nitrogen atoms and form pyridinic and pyrrolic units. Our in situ studies show that the photolysis products of acetonitrile depend on the photon irradiation duration and composition of the initial CFx matrix. The obtained results evaluate the radiation damage of the acetonitrile-intercalated fluorinated graphites and the opportunities to synthesize nitrogen-doped graphene materials.

Calcite Nanotuned Chitinous Skeletons of Giant Ianthella basta Marine Demosponge

Marine sponges were among the first multicellular organisms on our planet and have survived to this day thanks to their unique mechanisms of chemical defense and the specific design of their skeletons, which have been optimized over millions of years of evolution to effectively inhabit the aquatic environment. In this work, we carried out studies to elucidate the nature and nanostructural organization of three-dimensional skeletal microfibers of the giant marine demosponge Ianthella basta, the body of which is a micro-reticular, durable structure that determines the ideal filtration function of this organism. For the first time, using the battery of analytical tools including three-dimensional micro—X-ray Fluorescence (3D-µXRF), X-ray diffraction (XRD), infra-red (FTIR), Raman and Near Edge X-ray Fine Structure (NEXAFS) spectroscopy, we have shown that biomineral calcite is responsible for nano-tuning the skeletal fibers of this sponge species. This is the first report on the presence of a calcitic mineral phase in representatives of verongiid sponges which belong to the class Demospongiae. Our experimental data suggest a possible role for structural amino polysaccharide chitin as a template for calcification. Our study suggests further experiments to elucidate both the origin of calcium carbonate inside the skeleton of this sponge and the mechanisms of biomineralization in the surface layers of chitin microfibers saturated with bromotyrosines, which have effective antimicrobial properties and are responsible for the chemical defense of this organism. The discovery of the calcified phase in the chitinous template of I. basta skeleton is expected to broaden the knowledge in biomineralization science where the calcium carbonate is regarded as a valuable material for applications in biomedicine, environmental science, and even in civil engineering.

The Identification of Cu–O–C Bond in Cu/MWCNTs Hybrid Nanocomposite by XPS and NEXAFS Spectroscopy

The results of the research of a composite based on multi-walled carbon nanotubes (MWCNTs) decorated with CuO/Cu2O/Cu nanoparticles deposited by the cupric formate pyrolysis are discussed. The study used a complementary set of methods, including scanning and transmission electron microscopy, X-ray diffractometry, Raman, and ultrasoft X-ray spectroscopy. The investigation results show the good adhesion between the copper nanoparticles coating and the MWCNT surface through the oxygen atom bridge formation between the carbon atoms of the MWCNT outer graphene layer and the oxygen atoms of CuO and Cu2O oxides. The formation of the Cu–O–C bond between the coating layer and the outer nanotube surface is clearly confirmed by the results of the O 1s near edge X-ray absorption fine structure (NEXAFS) and X-ray photoelectron spectroscopy (XPS) of the Cu/MWCNTs nanocomposite. The XPS measurements were performed using a laboratory spectrometer with sample charge compensation, and the NEXAFS studies were carried out using the synchrotron radiation of the Russian–German dipole beamline at BESSY-II (Berlin, Germany) and the NanoPES station at the Kurchatov Center for Synchrotron Radiation and Nanotechnology (Moscow, Russia).

Spectral studies of bismuth-containing pyrochlores

Thermal stable solid solutions of titanates, niobates, and tantalates of bismuth with a pyrochlore structure doped with 3d-metal atoms were studied using XPS and NEXAFS spectroscopy. Based on spectral studies, it was shown that the manganese, cobalt, nickel and copper atoms in these solid solutions have mainly charge state +2 and iron atoms – charge state +3.

NEXAFS study of carbonate substituted bioapatite

The investigation of unique carbonate substituted bioapatite of Champsocephalus gunnari icefish jaw and skull bones was carried out using NEXAFS spectroscopy. It has been established that these bones contain the B-type carbonate substituted hydroxyapatit with a content [CO3]2- anion of about 0.79-3.07 wt.%.

Characterizing porous microaggregates and soil organic matter sequestered in allophanic paleosols on Holocene tephras using synchrotron-based X-ray microscopy and spectroscopy

Allophanic tephra-derived soils can sequester sizable quantities of soil organic matter (SOM). However, no studies have visualized the fine internal porous structure of allophanic soil microaggregates, nor studied the carbon structure preserved in such soils or paleosols. We used synchrotron radiation-based transmission X-ray microscopy (TXM) to perform 3D-tomography of the internal porous structure of dominantly allophanic soil microaggregates, and carbon near-edge X-ray absorption fine-structure (C NEXAFS) spectroscopy to characterize SOM in ≤ 12,000-year-old tephra-derived allophane-rich (with minor ferrihydrite) paleosols. The TXM tomography showed a vast network of internal, tortuous nano-pores within an allophanic microaggregate comprising nanoaggregates. SOM in the allophanic paleosols at four sites was dominated by carboxylic/carbonyl functional groups with subordinate quinonic, aromatic, and aliphatic groups. All samples exhibited similar compositions despite differences between the sites. That the SOM does not comprise specific types of functional groups through time implies that the functional groups are relict. The SOM originated at the land/soil surface: ongoing tephra deposition (intermittently or abruptly) then caused the land-surface to rise so that the once-surface horizons were buried more deeply and hence became increasingly isolated from inputs by the surficial/modern organic cycle. The presence of quinonic carbon, from biological processes but vulnerable to oxygen and light, indicates the exceptional protection of SOM and bio-signals in allophanic paleosols, attributable both to the porous allophane (with ferrihydrite) aggregates that occlude the relict SOM from degradation, and to rapid burial by successive tephra-fallout, as well as strong Al-organic chemical bonding. TXM and C NEXAFS spectroscopy help to unravel the fine structure of soils and SOM and are of great potential for soil science studies.

Characterization of porous microaggregates and soil organic matter sequestered in allophanic paleosols on Holocene tephras using synchrotron-based X-ray microscopy and spectroscopy

Allophanic tephra-derived soils can sequester sizable quantities of soil organic matter (SOM). However, no studies have visualized the fine internal porous structure of allophanic soil microaggregates, nor studied the carbon structure preserved in such soils or paleosols. We used synchrotron radiation-based transmission X-ray microscopy (TXM) to perform 3D-tomography of the internal porous structure of allophanic soil microaggregates, and carbon near-edge X-ray absorption fine-structure (C NEXAFS) spectroscopy to characterize SOM in ≤12,000-yr-old tephra-derived allophanic paleosols. The TXM tomography showed a vast network of internal, tortuous nano-pores within an allophanic microaggregate comprising nanoaggregates. SOM in the allophanic paleosols at four sites was dominated by carboxylic/carbonyl functional groups with subordinate quinonic, aromatic, and aliphatic groups. All samples exhibited similar compositions despite differences between the sites. That the SOM does not comprise specific types of functional groups through time implies that the functional groups are relict. The SOM originated at the land/soil surface: ongoing tephra deposition (intermittently or abruptly) then caused the land-surface to rise so that the once-surface horizons were buried more deeply and hence became increasingly isolated from inputs by the surficial/modern organic cycle. The presence of quinonic carbon, from biological processes but vulnerable to oxygen and light, indicates the exceptional protection of SOM and bio-signals in allophanic paleosols, attributable both to the porous allophane aggregates that occlude the relict SOM from degradation, and to rapid burial by successive tephra-fallout, as well as strong Al-organic chemical bonding. TXM and C NEXAFS spectroscopy unravel the fine structure of soils and SOM and are of great potential for soil science studies.